Treatment of tanned leathers



United. States Patent 3,079,211 TREATMENT OF TANNED LEATHERS MaximoPaquet, Route de Nice, Cuers (Var), France No Drawing. Filed Sept. 28,1959, Ser. No. 842,605 Claims priority, application France Mar. 23, 195619 Claims. (Cl. 8-94.21)

The present invention relates to the treatment of leathers tanned withzirconium based tanning baths, with a view to controlling their waterabsorbing properties as well as their permeability to air.

This is a continuation-in-part of my co-pending application Serial No.641,458, filed February 21, 1957, now abandoned.

It has been found and verified since a number of years that tanning withzirconium, when properly conducted can produce leathers which are veryresistant to wear and friction. However, such leathers have the seriousdrawback of absorbing too high quantities of water, which restrictedtheir use. Various attempts have been made in different directions todecrease the said water absorption but such attempts have led either toa destruction of the favorable properties resulting from zirconiumtanning, or to make the treated leathers impervious to air, and finallyno satisfactory solution has been found.

The object of my invention is to provide zirconium tanned leathers thewater absorption qualities of which are conveniently controlled withoutimpairing their perviousness to air, or their resistance to wear.

I have found that if fibers of zirconium tanned leather are put incontact with higher fatty amines in proper conditions, the said aminesform with the acid reacting, tanning zirconium compounds which are fixedon said fibers, highly water repellent compounds which are also solidlyfixed on the fibers and which durably impart their water repellancy tothe treated leather. It would seem that an inversion of electric chargesoccurs, although this is a mere supposition.

The fatty amines which are operative in my invention are the long chainprimary amines derived from fatty acids, of the general formula R.NH inwhich R is an unsubstituted aliphatic chain having from 8 to 22 carbonatoms. Such amines may be considered as deriving from ammonia throughreplacement of one hydrogen atom by a fatty chain Without any othersubstitution.

Appropriate amines are caprylylamine (C Caprylamine (C laurylamine (Cmyristylarnine (C palmytylamine (C stearylamine (C oleylamine (Carachidylamine (C behenylamine (C and the like, the above list not beinglimitative. The average molecule weights of said amines range from about130 to about 320.

Although all the above amines give favorable results the best resultsare obtained with oleylamine or palrnytylamine, and natural orartificial mixtures of various amines having 16 or 18 carbon atoms maybe used satisfactorily in my invention. For example, I obtain goodresults with the mixture of oleylamine stearylamine and palmytylaminewith a dominant proportion of oleylamine, as obtained when treatingcommercial fatty acids.

Generally speaking, I prefer using amines derived from unsaturated fattyacids such as oleic or linoleic acids, rather than amines deriving fromsaturated acids. However, mixtures containing both types of amines aresuitable, and in fact often necessary when special detail eifects aredesired.

By commercial higher aliphatic or fatty amines, I mean herein productsof the modern chemical industry obtained by treating with ammonia, fattyacids having C to C chains, whether alone or in natural mixtures, inliquid or gaseous phase, at a given temperature and in suitableconditions. Intermediary products are thus ob tained, to wit nitriles,which are thereafter hydrogenated to the commercial fatty amines used inmy invention. The intermediary nitriles give no results in the methodaccording to my invention.

The above defined amines are neither pure products, nor products whichcan he defined other than by their method of manufacture but the primaryamines of the fatty acids employed are largely dominant, which issufficient for my process.

It is neither recommended nor necessary to use more complicated aminesthan those above-mentioned, e.g. amines comprising multiple orconjugated linkages, no particular or favourable effects being obtainedtherewith.

Although the above defined amines alone are adapted to give the desiredresults, I have found that the diamines of the same above mentionedfatty acids, which diamines are obtained by similar methods and often inmore or less great quantities at the same time as the primary aminesalso give satisfactory results and may be used in conjunction with saidprimary amines. Said diamines may be represented by the general formula:

in which R has the same meaning as above. The said diamines thuscomprise both a primary amine group and a secondary amine group. Likethe above mentioned primary fatty amines, they are strong bases and theyhave similar general properties with however a more pronounced polarityand a stronger cationic character.

It would appear that most of the commercial fatty amines, due to theirmethod of preparation, contain more or less important quantities of suchdiamines.

All the above mentioned amines and diamines are solid or liquidaccording to the degree of saturation of the fatty chain, and to theirmolecular weight. They are insoluble in water and soluble in mineraloils, in hydrocarbons, more particularly when added with alcohol, inethyl, methyl, isopropyl alcohols and the like, and in chlorinatedsolvents such as trichlorethylene, perchlorethylene or carbontetrachloride. All said amines and diamines react with organic ormineral acids to give salts the properties of which largely depend onthe acid which is used. Thus, most 'of the monoacids such ashydrochloric, acetic, formic, lactic acids and the like give watersoluble salts. The chlorides are soluble in water and soluble in oilswhereas the acetates and formates are soluble both in water and inhydrocarbons, as well as in chlorinated solvents.

Organic or mineral diacids of higher polyacids generally give saltswhich are insoluble in water and variously soluble in various solvents.

According to my invention, leathers must be treated by amines of theabove mentioned type, which have been wholly or partly neutralized by anacid or acids, because of their strongly basic properties, the saidneutralized amines being dissolved either in water or in organicsolvents depending on the neutralizing acid and the results which it isdesired to achieve.

I have found that the solutions in organic solvents should be preferredfor the treatment of thick leathers, whereas aqueous solutions may beused for the treatment of thin or highly porous leathers.

More particularly for the treatment of thick or heavy zirconium tannedleathers, the amines or mixtures of amines and diamines are dissolved inan organic solvent or a mixture of such solvents, then neutralized byadding to said solution one or more convenient acids.

Preferred amines are oleylamine, linoleylamine, palmytylamine andstearylamine or mixtures thereof and the solvent should preferably betrichloroethylene or a hydrocarbon.

I have found that for neutralizing the amine or amines, tartaric acidshould be used in a quantityv equal to at least half the total quantityof acid which is necessary for complete neutralization. The said acidshould be preferably added in powdered form, while stirring, to theamine solution maintained between 60 and 70 C. The reaction isexothermic and care should be taken to avoid a temperature rise above 80C. which could result in an unfavorable transformation of amines intoamides.

I have also found that part of the basicity of the amines mayadvantageously be neutralized by means of very weak acids such as phenicacid (phenol) or abietic acid (-colophane). V

The presence of such weak acids is useful even when the amines arecompletely neutralized by means of tartaric acid.

Tartaric acid may be inipartreplaced by citric, sulfuric, sulfurous orphosphoric acid. Cresol'may be used instead of phenol and any otherresin having .anacid reaction instead of abietic'acid.

I have furthermore found thatithe addition of a small quantity of boricacid to the tartaric acid substantially improves the results obtained.It:seems that boro-tartaric acid is formed, which acts favorably as acatalyst .of the va'rioussubsequent reactants in the presence ofbasicity of the amines;

The boric acid should amount to between and 20% of the quantity oftartaric acid;

The phenol (C H OH) or cresol should comprise between 10% and 50% of thetotal quantity of amines existing in the solution, this total beingcalculated in pure amines (according to their quantitative basicity);

The abietic acid should preferably comprise between 20% and 90% of thesame total weight of the amines.

These solutions in trichlor-ethylene are stable at temperatures which donot exceed 75 C. They are characterised by a high fluidity, a highdegree of penetration into the leather or other porous materials, and bytheir special properties of becoming fixed on products having an acidreaction.

For the treatment of heavy leathers tanned with zirconium, thesesolutions should be employed with a content of amines (calculatedin pureamines) comprised between 3% and of their weight.

The leathers tanned with zirconium or with mixed mineral tannings,brought to a pH value between 3.5 and 5.0, carefully washed and thendried or almost, dried, are soaked for 10 to 40 minutes in the solutiondescribed above, maintained between 15 and 50 0, depending on the case,and then dried in air at a temperature not exceeding 40 C.

The results are improved by operating in a closed tank in which acertain depression is maintained, for example 30 cm. of mercury. Thesolvent may be recuperated by drying in an appropriate apparatus with'orwithout vacuum.

The leathers thus treated and dried are already strongly water-repellentand can be used commercially in that state in certain caseshf They havehowever generally been subjected to excessive dehydration, whichmodifies prised as required between 12% and 18%.

This. hydrolysis is effected by soaking the leathers as treated 'aboveand dried for one hour or more, in a bath of water maintained between 40and 50 C. During the course of this operation, the appearance and colourof the leathers change completely and their water-repellentcharacteristics are considerably increased after they have again beendried.

To this bath of water, there may be added when so required, smallquantities of particular reagents (for example various organic acids) soas to modify certain details relative to qualities and appearance.

The application of the invention is illustrated in the examples given inthe following text. These examples are understood to be illustrativeonly, and the invention is in no way limited by the indications giventherein.

Example 1 Heavy butts of cow leather are strongly tanned with zirconiumfollowing a standard method with a very acid pH value (about 1.5) andwith about 6.5% of zirconium oxide calculated on the weight of leatherbutts in strips.

The completely tanned skins are. rendered basic in a tanning bat-h up toa pH value of about 3.0 and are then .neutralized in a fresh bath to apH-value of 4.0 to 4.5

and carefully washed.

If so desired, they are then "rapidly surface-dyed by soaking for aboutone hour in a light bath of a vegetable tanning extract (for examplechestnut) so as to obtain a pleasing appearance. The leathers are thenallowed to drain, dried and then rolled. They give by analysis about 15%humidity.

At this stage, the leathers, show a water absorption of 65% to 70% withthe Kubelka apparatus in one hour, and have an excellent resistance towear.

The leathers are then treated as below so as to render themwater-repellent and to givethem special qualities. For this purpose, animpregnating solution A is made:

In. 1200 kg. of trichlor-ethylene there is dissolved while heating to 60C.: .kg. of commercial oleyl-amine containing 92 kg. of primary fattyamines composed of palmitylamine 7 kg, stearyl-amine 4 kg. oleyl-amine81 kg, the average molecular Weight of these amines being 268. Theestimation of the basicity showed that 29.6 kg. of pure tartaric acidwould be necessary to obtain complete neutralization.

To this solution, kept at 60 (3., there is slowly added: 25 kg. oftartaric acid and 2.5 kg. of boric acid,'both these acids being in theform of powder.

After complete reaction, which requires about 12 hours,

'28 kg. of phenol are added, followed by 47.5 kg. of

colophane.

After leaving to rest for .3 days, this solution A is ready for use.There is thus available about 1400 kg.

' of a solution containing about 6.6% of oleyl-amine, 2%

9 to 10% in l hour :16 to 18% in3 hours 34 to 38% in 24 hours Theimpregnated and normally-dried leathers giveon analysis a humiditycontent of 8 to 10%.

The gluing of these leathers with neoprene glues is possible, butnecessitates very extensive carding of the surfaces.

ExampleZ The, leathers obtained by the treatment of Example 1 are againtreated to give a hydrolysis. To this end, they are soakedfor one and ahalf hours in a bath of water held at 45 C., after which they are driedin air between and 35 C.

After drying, their colour is much lighter and more uniform and theirappearance is definitely more pleasing. With the Kubelka apparatus, theygive the following degrees of water absorption:

5 to 7% in 1 hour 8 to 9% in 3 hours 26 to 29% in 24 hours When normallydried, these leathers give 14 to 16% humidity on analysis: they canreadily be glued.

Example 3 100 kg. of the same zirconium leathers are impregnated withthe same solution A, but this operation is carried out in a suitabletank, in which is maintained a temperature of 45 C., and a depression ofabout 30 cm. of mercury. The period of impregnation is. minutes, afterwhich the solution is evacuated and the leathers are left in the tank.The solvent is then evaporated in the tank itself, in which is maintained 'adepre'ssion or 10 to 20 cm. of mercury. fAfte'r'40 minutes ina suitable apparatus, about 90% of the solvent used for the impregnationis recovered in this way.

The leathers are removed from the tank and completely dried in air atabout C.

After leaving to rest in this state, a hydrolysis treatment is made, asin Example 2 above, but with water at C. to which there has been added 1part in 10,000 of its weight of ethylene-diamine tetracetic acid. Theleathers thus obtained and dried are of very light colour and pleasantappearance. It is found by analysis that they have fixed 3.5% of fattyamines and that they have an average humidity of 14 to 16%.

With the Kubelka apparatus, these leathers give greatly improvedwater-absorption characteristics as follows:

3 to 5% in 1 hour 7 to 8% in 3 hours '22 to 24% in 24 hours Theseleathers can be glued perfectly and without any difiiculty. Togetherwith a very low water-absorption characteristic, they have an excellentand substantially increased resistance to wear together with mechanical,physical and chemical properties which are both new and very favorable,in particular exceptional resistance to pulling ofi, tearing andabrasion.

Example 4 The same process is followed as for Example 3, but theimpregnating solution employed is obtained with the following mixture:

Commercial oleyl-amine: Commercial stearyl-diamine: 50%

For the neutralization of 100 kg. of this mixture, the quantity oftartaric acid is brought up to 29 kg., the other constituents remainingunchanged.

The impregnating operation and the hydrolysis process are the same asfor Example 3.

The results obtained are also comparable with those obtained in Example3, namely:

Similar water absorption characteristics;

The leathers are darker with a more greasy appearance;

The leathers are softer and more flexible;

The resistance to tearing is exceptionally high.

ExampleS The same process is followed as in Example 3, but theimpregnating solution is obtained by using the mixture of fatty aminesresulting from the treatment of a mixture of fatty acids fromordinarytallow. This mixture contains:

About 30% About 40% About 30% The neutralization of the solution isobtained as in Example 3, the other constituents remaining unchanged.

The operation of impregnation and hydrolysis are effected in the sameway as in Example 3.

The results obtained are closely similar to those described in Example3, but the leathers are stiffer, their appearance is less pleasing, andthe favorable effects of hydrolysis are reduced.

of palrnityl-amine of oleyl-amine of stearyl-amine Example 6 The sameprocess is employed as for Example 3, but the impregnating solution isobtained by utilizing the mix- .ture of fatty amines resulting from thetreatment of the natural mixture of fatty acids in copra oils. Thismixture gives on analysis the following approximate composition:

' Percent Caprylyl-amine (C 8 Capryl-amine (C v9 Lauryl-amine (C 47Myristyl-amine (C l8 Palmity1-amine(C 8 Stearyl-amine (C 5 Oleyl-amine(C 5 The average molecular Weight of these amines is 196.

The'neutralization of the solution is carried out as in Example 3, withthe exception that 32 kg. of tartaric acid are added to kg. of the aboveamines in solution; the other constituents remain unchanged.

The operations of impregnation and hydrolysis are the same as in Example3.

The leathers obtained give the following water-absorptioncharacteristics with the Kubelka apparatus:

12 to 15% in 1 hour 18 to 20% in 3 hours 36 to 42% in 24 hours Thewater-repellent effects are definitely less than in the case of Example3, but they will often be adequate. The leathers are flexible, light incolour and of very pleasant appearance.

Example 7 The same process is followed as in Example 3, but theimpregnating solution is obtained by employing the mixture of fattyamines resulting from the treatment of the fatty acids of hydrogenatedtallow, which are thus saturated fatty acids.

This rnixture of amines has the following approximate composition:

Percent Palmityl-am-ine 30 Stearyl-arnine 68 Oleyl-amine 2 Example 8 Thesame process is followed as in Example 3, but the impregnating solutionis obtained with a mixture of 7 any amines derived from commercial fattyacids with 20 to 22 atoms of carbon.

This mixture has the following approximate composition:

Percent Arachidyl-amine (C 56 Behenyl-amine (C 35 Stearyl-amine (C 3) .9

The average molecular weight of these amines is about 310.

The neutralization of the solution is carried out as in 'Example 3, butonly 20 kg. of tartaric acid are employed for 100 kg. of the aboveamines; the other constituents remain unchanged.

The operations of impregnation and hydrolysis are carried out in thesame way as in Example 3. The leathers obtained are very finm, of darkappearance and their of-oleyl-amine and mixtures of oleyl-amine andlinoleylamine (unsaturated fatty chains) give the most favorable resultsin'the majority of the usual cases, but the other amines may produceleathers which have certain characteristics specially suitable forparticular cases.

Example 9.-Replacement of a Part of the Tartaric Acid in the AboveExamples by Another Polyvalent Acid The same procedure is followed as inExample 3 above. The impregnating solution is obtained ,with commercialoleyl-amine which gives by analysis the following composition:

Percent Oleyl-amine .85 ,Palmityl-amine 10 Stearyl-amine 5 The averagemolecular weight of the above amines is about 270.

The neutralization of the solution containing 100 kg. of these amines iscarried out as in Example 3, except in that the following are added:

Kg. Tartaric acid 1 Boric acid..." 2 Citric acid The above acids are inpowderform.

The other constituents remain unchanged.

The operations of impregnation and hydrolysis are also the same as inExample 3. The leathers obtained have similar characteristics to thoseof the leathers of Example- 3, with the following observations:

The water absorption percentages are higher;

The penetration of the amine compounds into the leather is less uniform,due to the greater viscosity of the impregnating solution;

The leathers have an excellent appearance.

From a large number of tests made by substituting another acid for partof the tartaric acid, the following conclusions have been reached:

The replacement of part of the tartaric acid by sulphuric acid,sulphurous acid, phosphoric acidand other polyvalent acids, takingaccount of their valency and their molecular weight, results insolutions the viscosity of which increases with the quantity of theseacids employed, while the penetration into the leathers diminishesrapidly. On the other hand, the water-repellent effects are favorable.

The replacement of part of the tartaric acid by .a monovalentacid-hydrochloric acid, acetic acid, formic acid, lactic acid, etc.,rapidly results in excessive water absorption as measured with theKubelka apparatus. This cffeet :can be employed to regulate the waterabsorption to any value desired, according to the case.

Example ]0.In7'tuence of the Solvent Used The same procedure is followedas in the case of Example 3, the same amines, same operations ofneutralization, and the same addition of the other constituents, but the1200 kg. of trichlor-ethylene (impregnating solution A) are replaced by750 kg. of ordinary benzene (density 0.9, boiling point 81 C.).

The operation of impregnation and hydrolysis are carried out as inExample 3.

The results obtained are in all respects very similar to those obtainedwith trichlor-ethylene employed as the solvent in Example 3, theconditions of recovery of the solvent and of drying being of courseappropriate to the solvent and the necessary precautions being taken inview of its inflammability.

It has been found that the results obtained with these leathers, withinthe framework of the present invention, vary very little with thesolvents employed, provided that the latter are taken from the family ofchlorinated solvents (tetrachlor-ethylene, perchlor-ethylene, carbontetrachloride, etc.), or from the'family of hydrocarbon solvents(benzene, toluene, naphtha solvents, etc.).

The choice of the solvent from the above groups should be made by takingaccount of their solvent qualities for the amine compounds, of theirphysical properties (density, boiling point, speed of evaporation,etc.), of their facility of use and of recovery within the scope oftheir. commercial utilization.

It has been found that alcohols can be employed as solvents, especiallywhen another solvent is added, since generally speaking, the alcoholsrapidly reduce the waterrepellent properties of the leathers treated,resulting in water absorption percentages, as given by the Kuibelkaapparatus, which rapidly become excessive with increasing proportions ofalcohol used as a solvent (ethyl alcohol, methyl alcohol, isopropylalcohol, etc.).

I claim:

1. A method for imparting water repellency to leathers tanned with azirconium based tanning bath, while maintaining high resistance to wearand high permeability to air, which comprises impregnating said leatherswith a solution in an organic solvent of compounds selected from thegroup consisting of a higher aliphatic primary amine of the generalformula R-NH and compounds selected from the group consisting of anamine of the general formula in which R is an aliphatic chain comprising8 to 22 carbon atoms and mixtures of said amines, said amines havingbeen previously combined with tartaric acid in at least one-half theamount required to neutralize said amine, and thereafter hydrolyzingsaid leathers by soaking in water at a temperature between about 25 and55 C., and drying said hydrolized leather in air.

2. A method as claimed in claim 1, in which the amine is commercialoleylamine.

3. A method as claimedin claim 1, in which the soaking solution is asolution of a mixture of amines derived from the fatty acids of copraoils, containing a major proportion of aliphatic chains containing 10,12 and 14 carbon atoms.

4. A method as claimed in claim 1, in which the soaking solution is a.solution of a mixture of primary fatty amines derived from the fattyacids of tallow having chains containing 16 and 18 carbon atoms, ofwhich fatty acids about 40% are constituted by oleic acid.

5. A method as claimed in claim 1, in which is used a mixture of primaryfatty amines derived from commercial oleic acid, said amines containinga proportion of at least 85% of oleyl-amine.

6. A method as claimed in claim 1, in which the seal;-

ing solution is a solution of a mixture of primary fatty amines derivedfrom hydrogenated tallow the predominating quantities in said aminemixture being constituted by stearyl-amine and palmityl-amine.

7. A method as claimed in claim 1, in which the soaking solution is asolution of a mixture of primary fatty amines having chains with 20 and22 atoms of carbon, the preponderant quantities in said amine mixturebeing constituted by arachidyl-amine and behenyl-amine.

8. A method as claimed in claim 1, in which said impregnating solutioncomprises quantities of fatty amines comprised between 3% and 18% byweight, calculated in pure amines before neutralization.

9. A method as claimed in claim 1, in which to said impregnated solutionare added the following:

10 to 40% of tartaric acid of the weight of the amines and diamines,calculated in pure amines or diamines;

from to 40% of phenol or cresol of the weight of the amines anddiamines, calculated in pure amines or diamines;

from to 90% of colophane of the weight of the amines and diamines,calculated in pure amines or diamines;

from 0 to 20% of boric acid, calculated on the Weight of tartaric acidused.

10. A method as claimed in claim 1, in which the solvent employed forsaid soaking solution is a chlorinated solvent.

11. A method as claimed in claim 1, in which the solvent employed forsaid soaking solution is a hydrocarbon.

12. A method as claimed in claim 1, in which the solvent employed forsaid soaking solution contains at least one alcohol in a proportion notexceeding 50%.

13. A method as claimed in claim 1, in which part of the tartaric acidemployed in said soaking solution is replaced by a polyvalent acidselected from the group consisting of citric acid, sulphuric acid,sulphurous acid, phosphoric acid, this substitution not exceeding 40% ofthe total quantity of acid necessary for the complete neutralization ofsaid amines.

14. A method as claimed in claim 1, in which at least a part of thetartaric acid employed in said impregnating solution is replaced by amonovalent acid selected from the group consisting of hydrochloric acid,acetic acid, formic acid, lactic acid, this substitution not exceedingof the quantity of acid necessary for the complete neutralization ofsaid amines.

15. A method as claimed in claim 1, in which the water employed for thehydrolysis of said leathers is acidified by the addition of a smallquantity of an acid.

16. A method as claimed in claim 15, in which said acid isethylene-diamine tetracetic acid.

17. A method for imparting water repellency to leather tanned with azirconium based tanning bath, while maintaining high resistance to wearand high permeability to air, which comprises impregnating said leatherswith a solution in an organic solvent of compounds selected from thegroup consisting of a higher aliphatic primary amine having an aliphaticchain of 8 to 22 carbon atoms and mixtures of said amines and previouslycombined with tartaric acid in at least one-half the amount required toneutralize said amine, said solution also containing phenol andcolophane and evaporating said solvent.

18. A method for imparting water repellency to leathers tanned with azirconium based tanning bath, while maintaining high resistance to wearand high permeability to air, which comprises impregnating said leatherswith a solution in an organic solvent of compounds selected from thegroup consisting of a higher aliphatic amine of the general formula inwhich R is an aliphatic chain comprising 8 to 22 carbon atoms andmixtures of said amines, said amine having been previously combined withtartaric acid in at least one-half the amount required to neutralizesaid amine, said solution also containing phenol and colophane.

19. A method as claimed in claim 18, in which the soaking solution is asolution of a mixture of primary fatty amines and fatty diamines, saidamines and diamines being constituted by fatty chains having from 12 to20 atoms of carbon.

References Cited in the file of this patent UNITED STATES PATENTS2,343,920 Maxwell Mar. 14, 1944 2,868,833 Szabo et al. Jan. 13, 1959FOREIGN PATENTS 452,630 Great Britain Aug. 21, 1936 OTHER REFERENCESJ.A.L.C.A., March 1959, page 178, vol. LIV, No. 3.

1. A METHOD FOR IMPARTING WATER REPELLENCY TO LEATHERS TANNED WITH AZIRCONIUM BASED TANNING BATH, WHILE MAINTAINING HIGH RESISTANCE TO WEARAND HIGH PERMEABILITY TO AIR, WHICH COMPRISES IMPREGNATING SAID LEATHERSWITH A SOLUTION IN AN ORGANIC SOLVENT OF COMPOUND SELECTED FROM THEGROUP CONSISTING OF A HIGHER ALIPHATIC PRIMARY AMINE OF THE GENERALFORMUL R-NH2 AND COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF ANAMINE OF THE GENERAL FORMULA